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Biomaterials

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Velcro Biomimetic Principle

The inventor of Velcro, George Mestral, was working in the machine shop of a Swiss engineering company more than 60 years ago. He examined the burrs that stuck to his dog’s fur under a microscope, and saw that they consisted of hundreds of tiny hooks that latched into the soft dog’s fur. He discussed the principle with weaving experts in the French cloth industry, and eventually a weaver produced cotton tapes that when pressed together fastened in the same manner as the teasel and fur.

This idea was patented by a Swiss company, Velcro S.A in 1952. These patents covered "the invention and fabrication of special napped piles of man-made material, at least some of these loops having the means of hooking near their ends".

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Velcro, SEM

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Velcro, SEM

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Shark Skin

Shark skin is very rough, in fact so rough that dried shark skin can be used as sanding paper. • The skin is covered by little V-shaped bumps, made from the same material as sharks' teeth. • The rough surface has been shown to reduce friction when the shark glides through water, which is why sharks are surprisingly quick and efficient swimmers.

Fabrics modelled on sharkskin designed to reduce drag by channeling the water along grooves in the fabric. These grooves allow the water to spiral in microscopic vortices, a hydrodynamic advantage. After looking at shark skin, NASA pioneered the use of longitudinal riblets, ridges perpendicular to surface, to reduce drag on flat surfaces of ships and aircraft. Ribletswere used successfully to reduce drag on the ‘Stars and Stripes’ America’s Cup yacht and were thought to offer such an advantage that riblets were banned from competition for subsequent events. Shark skin itself is far more complex than simple longitudinal riblets

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Biomaterials

Solid biomaterials produces by living organisms:Bones, teeth, spines, shells…

Substances prepared by biomimetic approaches or materials prepared for living/tissue interaction

Biomineralization:The mechanism by which living organisms form inorganic solids.

Differences between man-made analogues and “natural” synthesis:Exceptional control over shape, size and orientation.Not formed corresponding to thermodynamic/kinetic control as abiogenicmaterials.Extreme control over local environments (e.g. chemical composition)

•Mechanical properties•Chemical storage•Navigation

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Dominant: Calcium (due to low solubility)Silica: stability toward water.

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Tests (glass shells) offour radiolaria

Radiolarians are mostly marine and have glass shells.

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Vectorial (directional) and scalar (numerical) regularity in unicellular organisms : Acantharia (Radiolaria). In the above we discussed pattern formation by cell division (and in many cases followed by cell differentiation), and cell migration, and we saw that still some sort of pre-generated vectoriality must be assumed. And this is even more so when we consider unicellular organisms, especially those that are not simply drop-like (whose form can possiblybe explained by surface tension phenomena), but have a regular form of anisotropy, resulting in certain constantdirections being pronounced with respect to other directions. This we see very clearly in the case of the Acanthariawhich is a group of Radiolarians ( The latter are unicellular but complex planktonic marine organisms (smaller than1mm), in most cases possessing a skeleton (mineral or otherwise), wich often is very regular and consists ofperforated concentric spheres and/or radially placed needles).The skeleton of the Acantharia is made from strontium sulfate (SrSO4) and consists of 20 needles (often providedwith outgrowths) that are arranged according to 'Müller's Law' : If we imagine these needles as originating from thecenter of a sphere (such as the earth), then there are four arctic polar needles (going through the arctic circle), fournorthern tropic needles (going through the northern tropic), four equatorial needles (going through the equator), foursouthern tropic needles (going through the southern tropic) and, finally, four antarctic polar needles (going throughthe antarctic circle).

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Bloodworm teeth: Cu2(OH)3Cl, atacamite

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Sea Urchin spine

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Diatoms

Microscopic unicellular algae.Exoskeleton of amorphous SiO2

Deposits on ocean floor: used commercially (shoe polish, cosmetics…)

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Exoskeleton formation

Polycondenstion is suppressed by a Cofactor (Cof) (unknown)Silica transport vesicles (STV) transport the silica to the cell wall and mineralization takes place in silica deposition vesicles (SDV)Patterning is used to define the shape (mold-prepattern hypothesis)

Si undersaturated in sea water. Must be actively transported into the cell (monomeric).

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Bone: ordered mesoscopic crystalline aggregates

Structural material and ion reservoir.Both functions depend on the exact size, shape, chemical composition, and crystal structure of the mineral component, and on their arrangement in the organic matrix.

General composition:Ca8.3(PO4)4.3(CO3)x(HPO4)y(OH)0.3

y decrease and x increase with age (x+y ~ constant)

Nanocomposite material, different layers of organization from the nanoscopic to the macroscopic structure:

• Lowest: Crystals and the organic framework (collagen fibrils) and their relationship

• Tens of microns: longer range organization of collagen and associated crystals

• Highest: macroscopic structure of bones. Dense outer layers surrounding a less dense, porous tissue.

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Crystalline materials

Transition metals: Mainly iron (some manganese) play a role in biomineralization.Dominated by redox properties (energy source), an affinity for O, S and OH, and ease of hydrolyzation.Magnetic properties of mixed valent iron phases are used e.g. for navigation. Magnetite, Fe3O4 or greigite, Fe3S4. Size and shape is controlled by organic membranes.Aligned, single magnetic domain particles (40-80nm, ferromagnetic). Smaller crystals would be superparamagnetic, larger would be multidomain.

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Mineralization processes

Much is still unknown about the molecular interaction in the formation mechanisms of biominerals.Again, precipitation is easy, but controlling size, shape, orientation and assembly of the crystals is not…In biomineralization, the concentration and the nature of the interfaces (mineral-organic matrix and mineral-environment) are of extreme importance.

Mineralization takes place in open systems far from equilibrium!Localized compartments (vesicles) surrounded by lipid membranes are very common.Active accumulation of ions against concentration gradient require ion specific pumps or channels.

•Supramolecular preorganization•Controlled nucleation•Controlled crystal growth•Cellular processing

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Supramolecular preorganization

e.g. supramolecular reaction compartment. The mineralization zone is isolated from the cellular environment.

• On or in the membrane wall of bacterial cells (epicellularly)• Outside the cell. (e.g. collagen matrix of bone) Many shells or teeth are

constructed within lamellar, columnar or reticular frameworks.• Intracellularly by self-assembly. Construction of compartments are mainly

based on balancing hydrophilic-hydrophobic interactions.

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Controlled nucleation by interfacial molecular recognition

Controlled nucleation into the framework organized in the first stage. One of the key points in biomineralization.The organized pre-structures consist of functionalized surfaces. Blueprints for site directed inorganic nucleation.Electrostatic, structural, and stereo chemical recognition.Charge and polarity distribution, curvature…

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Concave surfaces are more active due to high concentration of active groups.Planar surfaces allow “biological epitaxy”:

Sometimes larger periodic structures may control inorganic nucleation.e.g. collagenes: Bone crystals nucleate in the interstices of crystalline assembly of collagen fibrils..

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Controlled crystal growth

Nucleation and growth in a supramolecular confined host may result in size limitations, but would not control the morphology

Morphology may be controlled by strict control of localized chemical environment.

Sometimes different polymorphs are grown in the same system, e,g. Fe2O3

nH2O, γ-FeOOH and Fe3O4 or calcite and aragonite in some shells.

Spatial localization of ion pumps in the compartment may shape the growing crystal by turning on and off ion flows.

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Cellular processing

Construction of higher order architectures.Example: Organized architecture found in nacre in shells. Plate-like aragonite crystals are organized with layers of sheet-like organic compounds. The organic layers are secreted out periodically during mineralization, resulting in a well organized lamellar structure.Details unknown…

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Synthetic biominerals

Implants or prostheses: attempts to replicate biological architecture. Currently not possible: Materials must be found to substitute biological materials.

Interaction between tissue and biomaterials:

• Bioinert materials. Minimal interaction with neighbouring tissue. Implants made of metal and porous alumina: cementing or screwing (morphological fixation)

• Biocompatible materials: Interact (positively) with neighboring tissue. Enhances the mechamical stability of the implant. (hydroxyapatite implants are mechanically attached by ingrowth) (biological fixation)

• Bioactive materials: Increase recovering and growth. Resorbable bioactive materials will be slowly replaced by bone. Bioactive, dense, nonporous surface reactive ceramics, glasses and glass ceramics. Attached by chemical bonding. (bioactive fixation)

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Materials

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Bioactive ceramics and glasses

Typical chemical compositions: Na2O, K2O, MgO, CaO, Al2O3, SiO2, P2O5, CaF2

Low silica and presence of calcium and phosphate: rapid ion exchange, rapid nucleation and crystallization of hydroxycarbonate apatite. (bone mineral)

Stages 1-5 fairly well understood… 6-11 not really

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Joint prostheses

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Biomimetic materials chemistry

Bioinspired materials processing

Complex structured composites; difficult to mimic. (so far very limited success.)No system has yet shown the level of control and complexity that is found in biogenic materials.Would be a significant step towards synthesis of “smart” materials.

Example: Microemulsion, phospholipid vesicles, proteins and reverse micelles. Formed by surfactant-water mixtures. Used for producing nanoparticles.e.g. magnetite crystals (Fe3O4)Variable dimensions (1-500nm), surface functional groups may be modified.

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Synthetic surfaces

Synthetic surfaces used for initializing nucleation. Use of surfactant monolayersor surfaces: functionality and packing may be tuned.

Example: formation of thin films and size controlled microcrystals of semiconducting sulfides.

Diffusion of H2S through a surfactant monolayer on an aqueous solution of a metal salt.Film formation in a layer-by-layer way.(CdS ~ 30 nm, ZnS ~ 350 nm)

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BaSO4

Normally rectangular tablets are obtained by precipitation of baryte, BaSO4.

When precipitated in the presence of a monolayer of n-eicosyl sulfate (C20H21OSO3

-) a morphological change is seen

Monolayers of n-eicosyl sulfate BaSO4 nucleate with the (100) face parallel to the monolayer. The arrangement of sulfate groups simulates the arrangement in baryte, leading to oriented nucleation

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Fusion of Seashell Nacre and Marine Bioadhesive Analogs:High-Strength Nanocomposite by Layer-by-Layer Assembly

of Clay and L-3,4-Dihydroxyphenylalanine Polymer**By Paul Podsiadlo, Zhongqiang Liu, David Paterson, Phillip B. Messersmith,

and Nicholas A. Kotov*Adv. Mater. 2007, 19, 949–955

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